EP0953025A1 - Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate - Google Patents

Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate

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Publication number
EP0953025A1
EP0953025A1 EP98955642A EP98955642A EP0953025A1 EP 0953025 A1 EP0953025 A1 EP 0953025A1 EP 98955642 A EP98955642 A EP 98955642A EP 98955642 A EP98955642 A EP 98955642A EP 0953025 A1 EP0953025 A1 EP 0953025A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
acrylate
copolymer
meth
tack
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP98955642A
Other languages
German (de)
French (fr)
Inventor
Eric Radigon
Jean Lebez
Jean-Michel Pierrot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema SA
Original Assignee
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0953025A1 publication Critical patent/EP0953025A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to a hot-melt adhesive based on a copolymer of ethylene and an alkyl (meth) acrylate.
  • Hotmelt are thermoplastic materials which are solid at room temperature and which, when heated, become viscous liquids. These viscous liquids are applied to a first substrate and then covered with a second surface. By cooling, an adhesion is obtained between the substrate and the second surface.
  • the open time is the period during which the adhesive which has been applied to a substrate which is at room temperature remains tacky, that is to say the time interval during which the second surface can be applied and by cooling to obtain adhesion between the substrate and the second surface.
  • HMA hot melt adhesives
  • Adhesives with infinite open time are required for self-adhesive labels or adhesive tapes used at room temperature. Depending on the nature of the adhesive, more or less strong adhesions can be obtained, for example peeling off and re-sticking the label. Bonding is carried out by pressure at room temperature. The adhesive is deposited on the substrate (for example label or tape) when hot.
  • HMPSA hot melt pressure sensitive adhesives
  • the present invention relates to these two types of hot-melt adhesives, that is to say HMA and HMPSA.
  • the HMPSAs are preferably based on block copolymers SIS (styrene-isoprene-styrene) but also SBS (styrene-butadiene-styrene).
  • ethylene- (meth) acrylate copolymers the alkyl group having at least 5 carbon atoms and advantageously 6 to 24 carbon atoms, make it possible to prepare HMPSA adhesives with properties essentially similar to those based on SIS or SBS while having better loop tack, better finger tack, better peel level than ethylene butyl acrylate copolymers.
  • the heavy (meth) acrylates of the 2-ethylhexyl acrylate type provide better resistance at low temperature by comparison with butyl or ethyl acrylate.
  • they are applicable at low temperature (COOL MELT), for example between 130 and 1 50.
  • the present invention is therefore a hot-melt adhesive comprising:
  • the adhesives of the HMPSA type are deposited hot (in fusion) on a substrate such as for example a paper tape, in polyamide, or polyolefinic or polyester substrate; by cooling, an adhesive face is obtained at room temperature.
  • a substrate such as for example a paper tape, in polyamide, or polyolefinic or polyester substrate
  • This adhesive side can be protected before use by a silicone paper or the other side of the substrate (winding of an adhesive tape on itself).
  • the loop tack test is the FINAT FTM 9 test described in the FINAT technical manual, Laan Copes Van Cattenbubch 79, NL 2585 EW LA HAYE (1 995) (HMPSA).
  • the tack is defined as being the force required to take off a loop of PET (Polyethylene terephthalate) coated with HMPSA, of which a determined surface has been previously brought into contact with a stainless steel plate.
  • the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 .
  • the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
  • the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH (relative humidity).
  • the self-adhesive tape is applied using a standard 2 kg standard roller.
  • the test is carried out using a dynamometer, at a traction speed of 300 mm / min in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
  • the loop-tack is quantified by the value of the maximum force.
  • the result of the loop tack measurement test is given in N / cm. The type of rupture must also be mentioned.
  • the rupture is undecided and one can observe on the same test tube the two types of ruptures described above.
  • FTM8 The creep resistance is determined by the FTM8 test (FINAT Manual already cited) (HMPSA).
  • the creep test measures the capacity of an HMPSA to resist a static force of 1 kgf at a given temperature (at room temperature in the examples of the present invention).
  • the static shear resistance is defined by the time necessary to separate by parallel vertical sliding an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
  • the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 .
  • the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
  • the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
  • the self-adhesive tape is applied using a standard 2 kg standard roller. The result of the creep test is given in minutes. The type of rupture must also be mentioned.
  • FTM1 The adhesion to steel is determined by the FTM1 test (FINAT Manual already mentioned) (HMPSA). This test quantifies the adhesive power. The latter is defined as the force required to remove a PET strip coated with HMPSA from a stainless steel plate.
  • the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 .
  • the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
  • the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
  • the self-adhesive tape is applied using a standard 2 kg standard roller. The adhesion strength is measured 20 minutes after application.
  • the test is carried out using a dynamometer, under a 180 ° peeling angle, at a speed of 300 mm / min in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
  • the cloud point is determined as follows: the glue is heated to 175 ° C., then a drop is placed on the bulb of a thermometer
  • ASTM ASTM then the temperature at which the haze appears during cooling is noted. A value below 50 ° C or 60 ° C indicates good compatibility between the constituents of the hot melt.
  • SAFT shear adhesion failure temperature
  • the SAFT test (ASTM D 4498) measures the capacity of a hot-melt adhesive to resist a static force of 0.5 kg (or 0.25 kg), under the effect of a regular rise in temperature of 0.4 ° C / min .
  • the SAFT is defined by the temperature at which one can observe a separation, by parallel vertical sliding of an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
  • the hot-melt adhesive is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 .
  • the thickness being constant, the grammage is between 1 8 g / m 2 and 22 g / m 2 .
  • the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
  • the self-adhesive tape is applied using a standard 2 kg standard roller.
  • the SAFT result is given in ° C. The type of rupture must be mentioned.
  • PET Polyethylene terephthalate
  • the copolymer (A) ethylene- (meth) acrylate is such that the alkyl group contains at least 5 carbon atoms.
  • the Applicant has indeed discovered that alkyls having at least 5 carbon atoms give tack to HMPSA and good properties at low temperature to HMA.
  • the alkyl can be linear, branched or cyclic. Advantageously, it comprises 6 to 24 carbon atoms.
  • alkyl (meth) acrylates mention may be made of 2-ethylhexyl (meth) acrylate and octyl acrylate.
  • the (meth) acrylate content is advantageously at most
  • the melt index can be between 0, 1 and 1000 and is preferably at least 200 (in g / 10 min according to ASTMD 1 238-73 conditions E at 190 ° C under a load of 2, 1 6 kg).
  • (A) can be a mixture of two copolymers (A-]) and (A2) of different MFIs.
  • ) has an MFI less than 10 and (A2) has an MFI greater than 10.
  • ) is between 1 and 3 and the MFI of (A2) is between 50 and 400 .
  • the adhesives of the invention contain one or more tackifying resins, at least one wax, optionally fillers and / or stabilizers.
  • the adhesives of the invention contain one or more tackifying resins, one or more plasticizers and optionally stabilizers.
  • Suitable tackifying resins are, for example, rosin, rosin esters, hydrogenated rosin, polyterpenes and derivatives, aromatic or aliphatic petroleum resins, hydrogenated cyclic resins. These resins typically have a ring ball softening temperature between 25 ° C and 180 ° C and preferably between 50 ° C and 135 ° C.
  • the amount of tackifying resin can be from 50 to 180 parts per 100 parts of (A) and preferably 100 to 150 parts.
  • Other examples of rosin derivatives are described in
  • rosin derivatives of those obtained by hydrogenation, dehydrogenation, polymerization, esterification. These derivatives can be used as such or in the form of polyol esters such as pentaerythritol, polyethylene glycol and glycerol esters.
  • tackifying resin of dicyclopentadienes.
  • the adhesives of the invention may contain waxes. They make it possible to adjust the fluidity, the open time and the setting time.
  • the waxes can be recovered during the refining of petroleum fractions. These are, for example, waxes consisting essentially of paraffinic hydrocarbons and containing sufficient amounts of branched, cyclic and aromatic hydrocarbons to be much less crystalline than paraffins. Synthetic waxes can also be used, such as FISCHER TROPSCH waxes.
  • the paraffin waxes used in the adhesives of the invention have a melting temperature above 50 ° C and preferably between 60 ° C and 70 ° C.
  • the amount of wax can be between 30 and 80 parts per 100 parts of copolymer (A).
  • the plasticizers which can be used in the adhesives of the invention are, for example, aromatic or naphthenic paraffinic mineral oils. They are essentially used to lower the viscosity and to provide tack.
  • the amount of plasticizer can be between 10 and 30 parts per 100 parts of (A).
  • plasticizer of phthalates, azelates, adipates, tricresyl phosphate and polyesters.
  • the adhesives of the invention may contain fillers. Mention may be made, as examples of fillers, of silica, alumina, glass, glass beads, calcium carbonates, fibers and metal hydroxides. These fillers must not reduce the tack or the mechanical properties of the glue after its application.
  • the quantity of charges can represent up to 100 parts per 100 parts of (A).
  • the hot-melt adhesives of the invention are prepared by mixing in the molten state at temperatures between 130 ° C. and 200 ° C. until a homogeneous mixture is obtained.
  • the mixing time can be of the order of 30 minutes to 3 hours.
  • the usual devices for thermoplastics can be used such as extruders, cylinders, Banbury or Brabender mixers, or propeller mixers.
  • SIS styrene-isoprene-styrene block copolymer containing 15% by weight of polystyrene sold by SHELL CHIMIE under the reference KRATON-D- 1,161 N.
  • E-2 EHA / 3 to 8 ethylene-2-ethylhexyl acrylate (2 EHA) copolymers with characteristics:
  • PERMALYN 5095 solid rosin glycerol ester (produced by HERCULES)
  • CATENEX N 956 aliphatic paraffinic oil produced by SHELL
  • IRGANOX 1010 phenolic antioxidant produced by CIBA
  • the following tables show the properties of the HMPSAs produced with SIS (not in accordance with the invention) and according to the invention with E-2 EHA copolymers.
  • the composition of the HMPSA is listed at the top of each table.
  • the column E-2 EHA / 7 means that it is an HMPSA based on the copolymer E-2 EHA / 7.
  • BA 40 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and MFI: 40 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 67 ° C.
  • BA 175 denotes a copolymer of ethylene butyl acrylate at 28% by weight of acrylate and of MFI: 1,75 (in g / 10 min at 1 90 ° C under a load of 2, 1 6 kg according to ASTM D 1 238) , Tg 80 ° C.
  • BA 02 denotes an ethylene butyl acrylate copolymer at 30% by weight of acrylate and of MFI: 2 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 78 ° C.
  • BA 320 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and of MFI: 320 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 66 ° C. Table 1
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate Table 2 35% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 25% Catenex N956
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack Table 4
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate
  • RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate

Abstract

The invention concerns a hot melt adhesive comprising: an ethylene-alkyl (meth)acrylate copolymer (A), the alkyl group containing at least 5 carbon atoms; at least a tackifier resin, optionally a plasticizer and optionally a wax. Said adhesive is hot-deposited on a substrate. Said products are used for making self-adhesive tapes and labels.

Description

ADHESIF THERMOFUSIBLE A BASE D'UN COPOLYMERE DE L'ETHYLENE ET HEAT-MELT ADHESIVE BASED ON ETHYLENE COPOLYMER AND
D'UN (METH)ACRYLATE D'ALKYLEOF AN ALKYL (METH) ACRYLATE
La présente invention concerne un adhésif thermofusible à base d'un copolymère de l'éthylène et d'un (méth)acrylate d'alkyle.The present invention relates to a hot-melt adhesive based on a copolymer of ethylene and an alkyl (meth) acrylate.
Les colles (adhésifs) thermofusibles sont des matériaux thermoplastiques solides à la température ambiante et qui par chauffage deviennent des liquides visqueux. Ces liquides visqueux sont appliqués sur un premier substrat puis on le couvre avec une seconde surface. Par refroidissement, on obtient une adhérence entre le substrat et la deuxième surface. Le temps ouvert est la période pendant laquelle la colle qui a été appliquée sur un substrat qui est à la température ambiante reste collante, c'est-à-dire l'intervalle de temps pendant lequel on peut appliquer la seconde surface et par refroidissement obtenir une adhérence entre le substrat et la seconde surface.Hotmelt (adhesives) are thermoplastic materials which are solid at room temperature and which, when heated, become viscous liquids. These viscous liquids are applied to a first substrate and then covered with a second surface. By cooling, an adhesion is obtained between the substrate and the second surface. The open time is the period during which the adhesive which has been applied to a substrate which is at room temperature remains tacky, that is to say the time interval during which the second surface can be applied and by cooling to obtain adhesion between the substrate and the second surface.
Passé ce délai du temps ouvert on ne peut plus obtenir une adhérence suffisante entre le substrat et la seconde surface.After this open time period, it is no longer possible to obtain sufficient adhesion between the substrate and the second surface.
Ces colles sont désignées par l'abréviation HMA (hot melt adhesives). Les adhésifs ayant un temps ouvert infini sont nécessaires pour les étiquettes autocollantes ou les rubans adhésifs utilisés à température ambiante. Selon la nature de l'adhésif on peut obtenir des adhérences plus ou moins fortes, par exemple décoller et recoller l'étiquette. Le collage s'effectue par pression à température ambiante. L'adhésif est déposé sur le substrat (par exemple étiquette ou ruban) à chaud. Ces adhésifs sont désignés par HMPSA (hot melt pressure sensitive adhesives), ils sont aussi désignés parfois comme des compositions thermofusibles auto-adhésives. La présente invention concerne ces deux types d'adhésifs thermofusibles c'est-à-dire les HMA et les HMPSA.These adhesives are designated by the abbreviation HMA (hot melt adhesives). Adhesives with infinite open time are required for self-adhesive labels or adhesive tapes used at room temperature. Depending on the nature of the adhesive, more or less strong adhesions can be obtained, for example peeling off and re-sticking the label. Bonding is carried out by pressure at room temperature. The adhesive is deposited on the substrate (for example label or tape) when hot. These adhesives are designated by HMPSA (hot melt pressure sensitive adhesives), they are also sometimes designated as self-adhesive hot-melt compositions. The present invention relates to these two types of hot-melt adhesives, that is to say HMA and HMPSA.
Selon l'art antérieur, voir par exemple ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, 5e édition (1 995) Vol A 26 p. 659-660, les HMPSA sont de préférence à base de copolymères blocs SIS (styrène-isoprène-styrène) mais aussi SBS (styrène-butadiène-styrène) .According to the prior art, see for example ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, 5th edition (1 995) Vol A 26 p. 659-660, the HMPSAs are preferably based on block copolymers SIS (styrene-isoprene-styrene) but also SBS (styrene-butadiene-styrene).
Dans le brevet US 5373041 concernant les HMPSA on a cité comme inconvénients des SBS et SIS leur instabilité à chaud et aux rayons U.V. ainsi que leur mauvaise résistance aux huiles. Il a donc été proposé dans ce brevet de remplacer les SBS et SIS par des copolymères constitués de 60 à 70 % (en poids) d'éthylène, 30 à 40 % d'acrylate de n-butyle et de 0 à 5 % d'acide (méth)acrylique pouvant être neutralisé par des ions métalliques. La demande WO 97/12007 décrit des HMPSA, à base de copolymère éthylène - acrylate d'alkyle. Les exemples ne concernent que l'acrylate de butyle.In patent US 5373041 concerning HMPSA, the disadvantages of SBS and SIS have been cited as their instability under hot conditions and to UV rays as well as their poor resistance to oils. It was therefore proposed in this patent to replace the SBS and SIS with copolymers consisting of 60 to 70% (by weight) of ethylene, 30 to 40% of n-butyl acrylate and 0 to 5% of (meth) acrylic acid which can be neutralized by metal ions. Application WO 97/12007 describes HMPSAs, based on ethylene - alkyl acrylate copolymer. The examples relate only to butyl acrylate.
On a maintenant découvert que des copolymères éthylène- (méth)acrylate d'alkyle, le groupe d'alkyle ayant au moins 5 atomes de carbone et avantageusement 6 à 24 atomes de carbone, permettaient de préparer des adhésifs HMPSA avec des propriétés essentiellement voisines de celles à base de SIS ou SBS tout en ayant un meilleur tack à la boucle (loop tack), un meilleur tack au doigt, un meilleur niveau de pelage que les copolymères éthylène acrylate de butyle.It has now been discovered that ethylene- (meth) acrylate copolymers, the alkyl group having at least 5 carbon atoms and advantageously 6 to 24 carbon atoms, make it possible to prepare HMPSA adhesives with properties essentially similar to those based on SIS or SBS while having better loop tack, better finger tack, better peel level than ethylene butyl acrylate copolymers.
Quant aux adhésifs de type HMA, les (méth)acrylates lourds de type acrylate de 2-éthylhexyle apportent une meilleure tenue à basse température par comparaison avec l'acrylate de butyle ou d'éthyle. De plus ils sont applicables à basse température (COOL MELT), par exemple entre 130 et 1 50.As for the HMA type adhesives, the heavy (meth) acrylates of the 2-ethylhexyl acrylate type provide better resistance at low temperature by comparison with butyl or ethyl acrylate. In addition, they are applicable at low temperature (COOL MELT), for example between 130 and 1 50.
La présente invention est donc un adhésif thermofusible comprenant :The present invention is therefore a hot-melt adhesive comprising:
• un copolymère (A) éthylène-(méth)acrylate d'alkyle, le groupe alkyle ayant au moins 5 atomes de carbone, • une résine tackifîante, éventuellement un plastifiant et éventuellement une cire. • a copolymer (A) ethylene- (meth) acrylate, the alkyl group having at least 5 carbon atoms, • a tackifying resin, optionally a plasticizer and optionally a wax.
Les adhésifs du type HMPSA sont déposés à chaud (en fusion) sur un substrat tel que par exemple un ruban en papier, en polyamide, ou substrat polyoléfinique ou en polyester ; par refroidissement on obtient une face adhesive à température ambiante. Cette face adhesive peut être protégée avant son usage par un papier siliconé ou l'autre face du substrat (enroulement d'un ruban adhésif sur lui-même) .The adhesives of the HMPSA type are deposited hot (in fusion) on a substrate such as for example a paper tape, in polyamide, or polyolefinic or polyester substrate; by cooling, an adhesive face is obtained at room temperature. This adhesive side can be protected before use by a silicone paper or the other side of the substrate (winding of an adhesive tape on itself).
Dans la suite du texte on fait référence à différents tests ou méthodes de mesure permettant de déterminer les propriétés des HMPSA et des HMA.In the rest of the text, reference is made to different tests or measurement methods making it possible to determine the properties of HMPSA and HMA.
FTM9 : Le test du tack à la boucle (loop tack) est le test FINAT FTM 9 décrit dans le manuel technique FINAT, Laan Copes Van Cattenbubch 79, NL 2585 EW LA HAYE ( 1 995) (HMPSA) .FTM9: The loop tack test is the FINAT FTM 9 test described in the FINAT technical manual, Laan Copes Van Cattenbubch 79, NL 2585 EW LA HAYE (1 995) (HMPSA).
Ce test caractérise l'adhésion instantanée ou "tack". Le tack est défini comme étant la force requise pour décoller une boucle de PET (Polyéthylène téréphtalate) enduite de HMPSA, dont une surface déterminée a été préalablement mise en contact avec une plaque d'acier inoxydable. Le HMPSA est enduit entre 140°C et 180°C sur une bande de PET de (25 *400)mm2. L'épaisseur étant constante, le grammage est compris entre 18 g/m2 et 22 g/m2. Les bandes à tester doivent être conditionnées au moins quatre heures avant l'essai dans une pièce climatisée à (23 ± 2) °C, (50 ± 5)% HR (humidité relative). Le ruban auto-adhésif est appliqué à l'aide d'un rouleau standard normalisé de 2 kg.This test characterizes instant adhesion or "tack". The tack is defined as being the force required to take off a loop of PET (Polyethylene terephthalate) coated with HMPSA, of which a determined surface has been previously brought into contact with a stainless steel plate. The HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 . The thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 . The test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH (relative humidity). The self-adhesive tape is applied using a standard 2 kg standard roller.
Le test est effectué à l'aide d'un dynamomètre, à une vitesse de traction de 300 mm/min dans une pièce climatisée à (23 ± 2) °C, (50 ± 5)% HR.The test is carried out using a dynamometer, at a traction speed of 300 mm / min in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH.
Le loop-tack est quantifié par la valeur de la force maximum. Le résultat du test de mesure du tack à la boucle est donné en N/cm. Le type de rupture doit être également mentionné.The loop-tack is quantified by the value of the maximum force. The result of the loop tack measurement test is given in N / cm. The type of rupture must also be mentioned.
Les différents types de rupture sont définis comme suit :The different types of failure are defined as follows:
Rupture adhesiveAdhesive failure
Le HMPSA n'adhère pas sur un des deux substrats. Rupture cohésiveHMPSA does not adhere to one of the two substrates. Cohesive rupture
On observe une rupture dans le joint de colle. Dans ce cas les deux substrats encollés entraînent une partie du joint lors de la traction.There is a break in the adhesive joint. In this case the two glued substrates entrain a part of the joint during traction.
Rupture mixteMixed break
La rupture est indécise et on peut observer sur une même éprouvette les deux types de ruptures décrits plus haut.The rupture is undecided and one can observe on the same test tube the two types of ruptures described above.
FTM8 : La tenue au fluage est déterminée par le test FTM8 (Manuel FINAT déjà cité) (HMPSA) .FTM8: The creep resistance is determined by the FTM8 test (FINAT Manual already cited) (HMPSA).
Le test de fluage mesure la capacité d'un HMPSA à résister à une force statique de1 kgf à une température donnée (à l'ambiante dans les exemples de la présente invention).The creep test measures the capacity of an HMPSA to resist a static force of 1 kgf at a given temperature (at room temperature in the examples of the present invention).
La résistance au cisaillement statique est définie par le temps nécessaire pour séparer par glissement vertical parallèle une aire de (25 x 25) mm2 enduite de HMPSA, d'une plaque d'acier inoxydable plane.The static shear resistance is defined by the time necessary to separate by parallel vertical sliding an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
Le HMPSA est enduit entre 140°C et 180°C sur une bande de PET de (25 x 400) mm2. L'épaisseur étant constante, le grammage est compris entre 18 g/m2 et 22 g/m2. Les bandes à tester doivent être conditionnées au moins quatre heures avant l'essai dans une pièce climatisée à (23 ± 2) °C, (50 ± 5) % HR. Le ruban auto-adhésif est appliqué à l'aide d'un rouleau standard normalisé de 2 kg. Le résultat du test de fluage est donné en minutes. Le type de rupture doit être également mentionné.The HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 . The thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 . The test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH. The self-adhesive tape is applied using a standard 2 kg standard roller. The result of the creep test is given in minutes. The type of rupture must also be mentioned.
FTM1 : L'adhérence sur l'acier est déterminée par le test FTM1 (Manuel FINAT déjà cité) (HMPSA). Ce test quantifie le pouvoir adhésif. Ce dernier est défini comme étant la force requise pour enlever une bande de PET enduite de HMPSA d'une plaque d'acier inoxydable.FTM1: The adhesion to steel is determined by the FTM1 test (FINAT Manual already mentioned) (HMPSA). This test quantifies the adhesive power. The latter is defined as the force required to remove a PET strip coated with HMPSA from a stainless steel plate.
Le HMPSA est enduit entre 140°C et 180°C sur une bande de PET de (25*400) mm2. L'épaisseur étant constante, le grammage est compris entre 18 g/m2 et 22 g/m2. Les bandes à tester doivent être conditionnées au moins quatre heures avant l'essai dans un pièce climatisée à (23 ± 2) °C, (50 ± 5) % HR. Le ruban auto-adhésif est appliqué à l'aide d'un rouleau standard normalisé de 2 kg. La force d'adhésion est mesurée 20 minutes après application.The HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 . The thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 . The test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH. The self-adhesive tape is applied using a standard 2 kg standard roller. The adhesion strength is measured 20 minutes after application.
Le test est effectué à l'aide d'un dynamomètre, sous un angle de pelage 180°, à une vitesse de 300 mm/min dans une pièce climatisée à (23 ± 2) °C, (50 ± 5) % HR.The test is carried out using a dynamometer, under a 180 ° peeling angle, at a speed of 300 mm / min in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH.
Le résultat du test de pelage est donné en N/cm. Le type de rupture doit être mentionné.The result of the peel test is given in N / cm. The type of rupture must be mentioned.
Point de trouble (HMA et HMPSA) :Cloud point (HMA and HMPSA):
Le point de trouble est déterminé comme suit : on chauffe la colle à 1 75 °C, ensuite une goutte est déposée sur le bulbe d'un thermomètreThe cloud point is determined as follows: the glue is heated to 175 ° C., then a drop is placed on the bulb of a thermometer
ASTM puis on note la température à laquelle le trouble apparaît au cours du refroidissement. Une valeur inférieure à 50°C ou 60°C indique une bonne compatibilité entre les constituants du hot melt.ASTM then the temperature at which the haze appears during cooling is noted. A value below 50 ° C or 60 ° C indicates good compatibility between the constituents of the hot melt.
Viscosité Brookfield (HMA et HMPSA) :Brookfield viscosity (HMA and HMPSA):
Mesurée à 170°C, aiguille 27 à 10 tours/minute selon ASTM D 3236. SAFT (shear adhésion failure température) (HMA et HMPSA)Measured at 170 ° C, needle 27 at 10 rpm according to ASTM D 3236. SAFT (shear adhesion failure temperature) (HMA and HMPSA)
Le test SAFT (ASTM D 4498) mesure la capacité d'un adhésif thermofusible à résister à une force statique de 0.5 kg (ou 0,25 kg), sous l'effet d'une montée régulière en température de 0.4°C/min.The SAFT test (ASTM D 4498) measures the capacity of a hot-melt adhesive to resist a static force of 0.5 kg (or 0.25 kg), under the effect of a regular rise in temperature of 0.4 ° C / min .
Le SAFT est défini par la température à laquelle on peut observer une séparation, par glissement vertical parallèle d'une aire de (25 x 25) mm2 enduite de HMPSA, d'une plaque d'acier inoxydable plane.The SAFT is defined by the temperature at which one can observe a separation, by parallel vertical sliding of an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
L'adhésif thermofusible est enduit entre 140°C et 180°C sur une bande de PET de (25 x 400) mm2. L'épaisseur étant constante, le grammage est compris entre 1 8 g/m2 et 22 g/m2. Les bandes à tester doivent être conditionnées au moins quatre heures avant l'essai dans une pièce climatisée à (23 ± 2) °C, (50 ± 5) % HR. Le ruban auto-adhésif est appliqué à l'aide d'un rouleau standard normalisé de 2 kg. Le résultat du SAFT est donné en °C. Le type de rupture doit être mentionné.The hot-melt adhesive is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 . The thickness being constant, the grammage is between 1 8 g / m 2 and 22 g / m 2 . The test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ± 2) ° C, (50 ± 5)% RH. The self-adhesive tape is applied using a standard 2 kg standard roller. The SAFT result is given in ° C. The type of rupture must be mentioned.
Tack au doigt (méthode interne) (HMPSA)Finger Tack (internal method) (HMPSA)
Ce test donne une idée de l'adhérence immédiate d'un HMPSA enduit sur un support en PET. La valeur de tack au doigt est comprise entre 0 et 3.This test gives an idea of the immediate adhesion of an HMPSA coated on a PET support. The finger tack value is between 0 and 3.
0 : tack nul,0: zero tack,
1 : tack insuffisant,1: insufficient tack,
2 : bon tack, 3 : tack excellent.2: good tack, 3: excellent tack.
Test du tack à la bille (Rolling bail tack) ASTM D 31 21 de 1 989 (HMPSA)Rolling bail tack ASTM D 31 21 of 1,989 (HMPSA)
Lors de la détermination du tack d'un adhésif selon la méthode du Rolling Bail Tack, une bille d'acier est lâchée en haut d'un plan incliné. Celle-ci accélère et roule le long d'une surface horizontale recouverte par le produit à tester. Le tack est déterminé en mesurant la distance parcourue par la bille avant qu'elle ne soit stoppée. AppareillageWhen determining the tack of an adhesive according to the Rolling Bail Tack method, a steel ball is dropped at the top of an inclined plane. This accelerates and rolls along a horizontal surface covered by the product to be tested. The tack is determined by measuring the distance traveled by the ball before it is stopped. Equipment
- Equipement muni d'un plan incliné de (20,0 ± 0,2) ° - Bille d'acier d'une masse de (5,60 ± 0,05)g- Equipment fitted with an inclined plane of (20.0 ± 0.2) ° - Steel ball with a mass of (5.60 ± 0.05) g
- Bandes de polyéthylènetéréphtalate (PET) enduites de produits à tester.- Polyethylene terephthalate (PET) strips coated with products to be tested.
Le copolymère (A) éthylène-(méth)acrylate d'alkyle est tel que le groupe alkyle contient au moins 5 atomes de carbone. La demanderesse a en effet découvert que des alkyles ayant au moins 5 atomes de carbone donnaient du tack aux HMPSA et de bonnes propriétés à basse température aux HMA.The copolymer (A) ethylene- (meth) acrylate is such that the alkyl group contains at least 5 carbon atoms. The Applicant has indeed discovered that alkyls having at least 5 carbon atoms give tack to HMPSA and good properties at low temperature to HMA.
L'alkyle peut être linéaire, ramifié ou cyclique. Avantageusement il comprend 6 à 24 atomes de carbone. A titre d'exemple de ces (méth)acrylates d'alkyle on peut citer le (méth)acrylate de 2-éthylhexyle et l'acrylate d'octyle.The alkyl can be linear, branched or cyclic. Advantageously, it comprises 6 to 24 carbon atoms. By way of example of these alkyl (meth) acrylates, mention may be made of 2-ethylhexyl (meth) acrylate and octyl acrylate.
La teneur en (méth)acrylate est avantageusement d'au plusThe (meth) acrylate content is advantageously at most
50 % et de préférence comprise entre 20 et 40 % en poids. L'indice de fluidité à l'état fondu (ou MFI) peut être compris entre 0, 1 et 1000 et est de préférence d'au moins 200 (en g/10 mn selon ASTMD 1 238-73 conditions E à 190°C sous une charge de 2, 1 6 kg).50% and preferably between 20 and 40% by weight. The melt index (or MFI) can be between 0, 1 and 1000 and is preferably at least 200 (in g / 10 min according to ASTMD 1 238-73 conditions E at 190 ° C under a load of 2, 1 6 kg).
On ne sortirait pas du cadre de l'invention en utilisant un mélange d'au moins deux copolymères éthylène-(méth)acrylate d'alkyle. Selon une autre forme de l'invention (A) peut être un mélange de deux copolymères (A-] ) et (A2) de MFI différents.It would not be departing from the scope of the invention to use a mixture of at least two ethylene- (meth) acrylate copolymers. According to another form of the invention (A) can be a mixture of two copolymers (A-]) and (A2) of different MFIs.
Avantageusement (A-| ) a un MFI inférieur à 10 et (A2) a un MFI supérieur à 10. Par exemple le MFI de (A-| ) est entre 1 et 3 et le MFI de (A2) est entre 50 et 400.Advantageously (A- |) has an MFI less than 10 and (A2) has an MFI greater than 10. For example the MFI of (A- |) is between 1 and 3 and the MFI of (A2) is between 50 and 400 .
S'agissant des HMA les adhésifs de l'invention contiennent une ou plusieurs résines tackifiantes, au moins une cire, éventuellement des charges et/ou des stabilisants.As regards HMAs, the adhesives of the invention contain one or more tackifying resins, at least one wax, optionally fillers and / or stabilizers.
S'agissant des HMPSA les adhésifs de l'invention contiennent une ou plusieurs résines tackifiantes, un ou plusieurs plastifiants et éventuellement des stabilisants.With regard to HMPSA, the adhesives of the invention contain one or more tackifying resins, one or more plasticizers and optionally stabilizers.
Des résines tackifiantes qui conviennent, sont par exemple la colophane, les esters de colophane, la colophane hydrogénée, les polyterpènes et dérivés, les résines de pétrole aromatiques ou aliphatiques, les résines cycliques hydrogénées. Ces résines ont typiquement une température de ramollissement bille anneau entre 25 °C et 180°C et de préférence entre 50°C et 135°C.Suitable tackifying resins are, for example, rosin, rosin esters, hydrogenated rosin, polyterpenes and derivatives, aromatic or aliphatic petroleum resins, hydrogenated cyclic resins. These resins typically have a ring ball softening temperature between 25 ° C and 180 ° C and preferably between 50 ° C and 135 ° C.
La quantité de résine tackifiante peut être de 50 à 180 parties pour 100 parties de (A) et de préférence 100 à 150 parties. D'autres exemples de dérivés de la colophane sont décrits dansThe amount of tackifying resin can be from 50 to 180 parts per 100 parts of (A) and preferably 100 to 150 parts. Other examples of rosin derivatives are described in
ULLMAN'S (cité plus haut) Vol A 23 p. 79 - 86, le contenu étant incorporé dans la présente demande.ULLMAN'S (cited above) Vol A 23 p. 79 - 86, the content being incorporated into the present application.
A titre de dérivés de la colophane on peut citer ceux obtenus par hydrogénation, deshydrogénation, polymérisation, estérification. Ces dérivés peuvent être utilisés tels quels ou sous forme d'esters de polyols tels que les esters de pentaerythritol, polyéthylène glycol et glycérol.Mention may be made, as rosin derivatives, of those obtained by hydrogenation, dehydrogenation, polymerization, esterification. These derivatives can be used as such or in the form of polyol esters such as pentaerythritol, polyethylene glycol and glycerol esters.
A titre de résine tackifiante on peut encore citer les dicyclopentadiènes.Mention may also be made, as tackifying resin, of dicyclopentadienes.
Les adhésifs de l'invention peuvent contenir des cires. Elles permettent d'ajuster la fluidité, le temps ouvert et le temps de prise.The adhesives of the invention may contain waxes. They make it possible to adjust the fluidity, the open time and the setting time.
Les cires peuvent être récupérées lors du raffinage de fractions pétrolières. Ce sont par exemple des cires consistant essentiellement en hydrocarbures paraffiniques et contenant des quantités suffisantes d'hydrocarbures, ramifiés, cycliques et aromatiques pour être beaucoup moins cristallines que des paraffines. On peut aussi utiliser des cires synthétiques telles que les cires FISCHER TROPSCH. Avantageusement, les cires de paraffines utilisées dans les colles de l'invention ont une température de fusion supérieure à 50°C et de préférence entre 60 °C et 70 °C.The waxes can be recovered during the refining of petroleum fractions. These are, for example, waxes consisting essentially of paraffinic hydrocarbons and containing sufficient amounts of branched, cyclic and aromatic hydrocarbons to be much less crystalline than paraffins. Synthetic waxes can also be used, such as FISCHER TROPSCH waxes. Advantageously, the paraffin waxes used in the adhesives of the invention have a melting temperature above 50 ° C and preferably between 60 ° C and 70 ° C.
La quantité de cire peut être comprise entre 30 et 80 parties pour 100 parties de copolymère (A).The amount of wax can be between 30 and 80 parts per 100 parts of copolymer (A).
Les plastifiants que l'on peut utiliser dans les adhésifs de l'invention sont par exemple des huiles minérales paraffiniques aromatiques ou naphténiques. Ils servent essentiellement à baisser la viscosité et à apporter du tack. La quantité de plastifiant peut être comprise entre 10 et 30 parties pour 100 parties de (A).The plasticizers which can be used in the adhesives of the invention are, for example, aromatic or naphthenic paraffinic mineral oils. They are essentially used to lower the viscosity and to provide tack. The amount of plasticizer can be between 10 and 30 parts per 100 parts of (A).
A titre de plastifiant on peut encore citer les phtalates, azelates, adipates, le phosphate de tricresyl et les polyesters.Mention may also be made, as plasticizer, of phthalates, azelates, adipates, tricresyl phosphate and polyesters.
S'agissant des HMA les adhésifs de l'invention peuvent contenir des charges. A titre d'exemples de charges, on peut citer la silice, l'alumine, le verre, les billes de verre, les carbonates de calcium, les fibres, et hydroxydes métalliques Ces charges ne doivent pas réduire le tack ni les propriétés mécaniques de la colle après son application. La quantité de charges peut représenter jusqu'à 100 parties pour 100 parties de (A) .As regards HMA, the adhesives of the invention may contain fillers. Mention may be made, as examples of fillers, of silica, alumina, glass, glass beads, calcium carbonates, fibers and metal hydroxides. These fillers must not reduce the tack or the mechanical properties of the glue after its application. The quantity of charges can represent up to 100 parts per 100 parts of (A).
Il est recommandé d'ajouter des stabilisants tels que les antioxydants, on peut utiliser les antioxydants habituels des thermoplastiques.It is recommended to add stabilizers such as antioxidants, we can use the usual antioxidants of thermoplastics.
Les colles thermofusibles de l'invention sont préparées par mélange à l'état fondu à des températures entre 1 30°C et 200°C jusqu'à ce qu'on obtienne un mélange homogène. La durée de mélange peut être de l'ordre de 30 minutes à 3 heures. On peut utiliser les dispositifs habituels des thermoplastiques tels que des extrudeuses, des cylindres, des mélangeurs Banbury ou Brabender, ou des mélangeurs à hélice.The hot-melt adhesives of the invention are prepared by mixing in the molten state at temperatures between 130 ° C. and 200 ° C. until a homogeneous mixture is obtained. The mixing time can be of the order of 30 minutes to 3 hours. The usual devices for thermoplastics can be used such as extruders, cylinders, Banbury or Brabender mixers, or propeller mixers.
ExemplesExamples
On a utilisé les produits suivants :The following products were used:
SIS : copolymère bloc styrène-isoprène-styrène contenant 15 % en poids de polystyrène vendu par SHELL CHIMIE sous la référence KRATON-D- 1 161 N.SIS: styrene-isoprene-styrene block copolymer containing 15% by weight of polystyrene sold by SHELL CHIMIE under the reference KRATON-D- 1,161 N.
E-2 EHA / 3 à 8 : copolymères éthylène-acrylate de 2-éthyl héxyle (2 EHA) de caractéristiques : E-2 EHA / 3 to 8: ethylene-2-ethylhexyl acrylate (2 EHA) copolymers with characteristics:
PERMALYN 5095 : ester de glycérol de colophane solide (produit par HERCULES)PERMALYN 5095: solid rosin glycerol ester (produced by HERCULES)
CATENEX N 956 huile paraffinique aliphatique (produite par SHELL) IRGANOX 1010 antioxydant phénolique (produit par CIBACATENEX N 956 aliphatic paraffinic oil (produced by SHELL) IRGANOX 1010 phenolic antioxidant (produced by CIBA
SPECIALITY CHEMICALS).SPECIALITY CHEMICALS).
Les tableaux suivants montrent les propriétés des HMPSA réalisés avec du SIS (non conforme à l'invention) et selon l'invention avec des copolymères E-2 EHA. La composition du HMPSA est rappelée en tête de chaque tableau.The following tables show the properties of the HMPSAs produced with SIS (not in accordance with the invention) and according to the invention with E-2 EHA copolymers. The composition of the HMPSA is listed at the top of each table.
Par exemple la colonne E-2 EHA/7 veut dire que c'est un HMPSA à base du copolymère E-2 EHA/7.For example, the column E-2 EHA / 7 means that it is an HMPSA based on the copolymer E-2 EHA / 7.
35 BA 40 désigne un copolymère éthylène acrylate de butyle à 35 % en poids d'acrylate et de MFI : 40 (en g/10 mn à 1 90°C sous une charge de 2, 1 6 kg selon ASTM D 1 238), Tg 67 °C.35 BA 40 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and MFI: 40 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 67 ° C.
28 BA 175 désigne un copolymère éthylène acrylate de butyle à 28 % en poids d'acrylate et de MFI : 1 75 (en g/10 mn à 1 90°C sous une charge de 2, 1 6 kg selon ASTM D 1 238), Tg 80°C.28 BA 175 denotes a copolymer of ethylene butyl acrylate at 28% by weight of acrylate and of MFI: 1,75 (in g / 10 min at 1 90 ° C under a load of 2, 1 6 kg according to ASTM D 1 238) , Tg 80 ° C.
30 BA 02 désigne un copolymère éthylène acrylate de butyle à 30 % en poids d'acrylate et de MFI : 2 (en g/10 mn à 1 90°C sous une charge de 2, 1 6 kg selon ASTM D 1 238), Tg 78 °C.30 BA 02 denotes an ethylene butyl acrylate copolymer at 30% by weight of acrylate and of MFI: 2 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 78 ° C.
35 BA 320 désigne un copolymère éthylène acrylate de butyle à 35 % en poids d'acrylate et de MFI : 320 (en g/10 mn à 1 90°C sous une charge de 2, 1 6 kg selon ASTM D 1 238), Tg 66°C. Tableau 135 BA 320 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and of MFI: 320 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 66 ° C. Table 1
35 % (Copolymère (A) ou SIS) - 40 % Permalyn 5095 - 25 % Catenex N956 0.2 % Irganox 101035% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 25% Catenex N956 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaque Tableau 2 35 % (Copolymère (A) ou SIS) - 40 % Permalyn 5095 - 25 % Catenex N956RA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate Table 2 35% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 25% Catenex N956
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaque * 3 : Fort tack - 2 : Tack moyen - 1 : Tack faible - 0 : Tack nulRA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
Tableau 3 30 % (Copolymère (A) ou SIS) - 40 % Permalyn 5095 - 30 % Catenex N956 - 0.2 % Irganox 1010Table 3 30% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 30% Catenex N956 - 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaque * 3 : Fort tack - 2 : Tack moyen - 1 : Tack faible - 0 : Tack nul Tableau 4 RA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack Table 4
30 % (Copolymère (A) ou SIS) - 40 % Permalyn 5095 - 30 % Catenex N956 0.2 % Irganox 101030% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 30% Catenex N956 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaque * 3 : Fort tack - 2 : Tack moyen - 1 : Tack faible - 0 : Tack nul RA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
Tableau 5Table 5
(15 % Copolymère (A-| ) + 15 % Copolymère (A2) ou 30 % SIS) - 40 % Permalyn 5095 - 30 % Catenex N956 0.2 % Irganox 1010(15% Copolymer (A- |) + 15% Copolymer (A2) or 30% SIS) - 40% Permalyn 5095 - 30% Catenex N956 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésiveRA: Adhesive failure - RC: Cohesive failure
RM : Rupture mixte adhesiveRM: Mixed adhesive rupture
(RA) : Rupture adhesive avec léger dépôt de matière sur la plaque (RA): Adhesive failure with slight deposit of material on the plate
Tableau 6Table 6
(15 % Copolymère (A-| ) + 15 % Copolymère (A ) ou 30 % SIS) - 40 % Permalyn 5095 - 30 % Catenex N956 0.2 % Irganox 1010(15% Copolymer (A- |) + 15% Copolymer (A) or 30% SIS) - 40% Permalyn 5095 - 30% Catenex N956 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaqueRA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate
Tableau 7Table 7
(15 % Copolymère (A<| ) + 15 % Copolymère (A2) ou 30 % SIS) - 40 % Permalyn 5095 - 30 % Catenex N956 - 0.2 % Irganox 1010(15% Copolymer (A <|) + 15% Copolymer (A2) or 30% SIS) - 40% Permalyn 5095 - 30% Catenex N956 - 0.2% Irganox 1010
RA : Rupture adhesive - RC : Rupture cohésive - RM : Rupture mixte adhesive (RA) : Rupture adhesive avec léger dépôt de matière sur la plaque RA: Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate

Claims

REVENDICATIONS
1 - Adhésif thermofusible comprenant : - un copolymère (A) éthylène-(méth)acrylate d'alkyle, le groupe alkyle ayant au moins 5 atomes de carbone.1 - hot-melt adhesive comprising: - an ethylene- (meth) acrylate copolymer (A), the alkyl group having at least 5 carbon atoms.
- au moins une résine tackifiante, éventuellement un plastifiant et éventuellement une cire.- at least one tackifying resin, optionally a plasticizer and optionally a wax.
Cet adhésif étant déposé à chaud sur un substrat.This adhesive being hot deposited on a substrate.
2 - Adhésif selon la revendication 1 dans lequel le groupe alkyle du (méth)acrylate d'alkyle a de 6 à 24 atomes de carbone.2 - Adhesive according to claim 1 wherein the alkyl group of the alkyl (meth) acrylate has from 6 to 24 carbon atoms.
3 - Adhésif selon la revendication 1 dans lequel (A) est un copolymère de l'éthylène et de l'acrylate de 2-éthylhéxyle.3 - Adhesive according to claim 1 wherein (A) is a copolymer of ethylene and 2-ethylhexyl acrylate.
4 - Adhésif selon l'une quelconque des revendications précédentes dans lequel la quantité de résine tackifiante est de 50 à 180 parties (en poids), de préférence 100 à 1 50 pour 100 parties de (A).4 - Adhesive according to any one of the preceding claims in which the amount of tackifying resin is from 50 to 180 parts (by weight), preferably 100 to 150 for 100 parts of (A).
5. Adhésif thermofusible auto adhésif (HMPSA) sensible à la pression selon l'une quelconque des revendications précédentes et comprenant5. Pressure-sensitive hot-melt adhesive (HMPSA) according to any one of the preceding claims and comprising
- le copolymère (A)- the copolymer (A)
- au moins une résine tackifiante - au moins un plastifiant- at least one tackifying resin - at least one plasticizer
- éventuellement des stabilisants.- possibly stabilizers.
6. Adhésif thermofusible (HMA) selon l'une quelconque des revendications 1 à 4 et comprenant : - le copolymère (A)6. Hot-melt adhesive (HMA) according to any one of claims 1 to 4 and comprising: - the copolymer (A)
- au moins une résine tackifiante- at least one tackifying resin
- au moins une cire- at least one wax
- éventuellement des stabilisants. - possibly stabilizers.
EP98955642A 1997-11-14 1998-11-12 Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate Ceased EP0953025A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9714320 1997-11-14
FR9714320 1997-11-14
PCT/FR1998/002409 WO1999025785A1 (en) 1997-11-14 1998-11-12 Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate

Publications (1)

Publication Number Publication Date
EP0953025A1 true EP0953025A1 (en) 1999-11-03

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ID=9513395

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98955642A Ceased EP0953025A1 (en) 1997-11-14 1998-11-12 Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate

Country Status (4)

Country Link
EP (1) EP0953025A1 (en)
AU (1) AU1241299A (en)
CA (1) CA2277787A1 (en)
WO (1) WO1999025785A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4238766A1 (en) 2022-03-04 2023-09-06 voestalpine Automotive Components Dettingen GmbH & Co. KG Method for connecting sheet metal parts to stacks of metal sheets and device for same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2819821B1 (en) * 2001-01-24 2005-01-14 Atofina USE OF A 2-ETHYLHEXYL ETHYLENE / ACRYLATE HMA FOR THE MANUFACTURE OF ARTICLES SUCH AS PACKAGING

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2739103B1 (en) * 1995-09-26 1998-08-28 Ceca Sa SELF-ADHESIVE THERMO-FUSE COMPOSITION BASED ON COPOLYMER ETHYLENE-ALKYL ACRYLATE AND ITS USE IN THE FIELD OF HYGIENE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9925785A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4238766A1 (en) 2022-03-04 2023-09-06 voestalpine Automotive Components Dettingen GmbH & Co. KG Method for connecting sheet metal parts to stacks of metal sheets and device for same

Also Published As

Publication number Publication date
AU1241299A (en) 1999-06-07
WO1999025785A1 (en) 1999-05-27
CA2277787A1 (en) 1999-05-27

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